Hemisynthesis, NMR Characterization and UHPLC-Q-Orbitrap /MS² identification of (+)-Catechin oxidation products in red wines and grape seed extracts

A unique “terroir” can be found in southern Bolivia, which combines the specific features of climate, topography and altitude of high valleys, with the management of grapevines staked on trees. It is one of the rare remnants of agroforestry viticulture. A survey was carried out among 29 grapegrowers in three valleys, to characterize the structure and management of these vineyards, and identify the services they expect from trees. Farms were small (2.2 ha on average) and 85% of vineyards were less than 1 ha. Viticulture was associated with vegetable, fruit and fodder production, sometimes in the same fields. Molle trees were found in all plots, together with one or two other native tree species. Traditional grapevine varieties such as Negra Criolla, Moscatel de Alejandría and Vicchoqueña were grown with a large range of densities from 1550 to 9500 vines ha-1. From 18 to 30% of them were staked on trees, with 1.2 to 4.9 vines per tree. The management of these vineyards (irrigation, fertilization and grapevine protection) was described, the most particular technical operation being the coordinated pruning of trees and grapevines. Three types of management could be identified in the three valleys. Grapegrowers had a clear idea of the ecosystem services they expected from trees in their vineyards. The main one was protection against climate hazards (hail, frost, flood). Then they expected benefits in terms of pest and disease control, improvement of soil fertility and resulting yield. At last, some producers claimed that tree-staking was quicker and cheaper than conventional trellising. It can be hypothesized then that agroforestry is a promising technique for the agroecological transition of viticulture. Its contribution to the “terroir” of the high valleys of southern Bolivia and its link with the specificities of the wines and spirits produced there remain to be explored.

In wine grape production, canopy management practices are applied to control the source-sink balance and improve the cluster microclimate to enhance berry composition. The aim of this study was to identify the optimal ranges of berry solar radiation exposure (exposure) for upregulation of flavonoid biosynthesis and thresholds for their degradation, to evaluate how canopy management practices such as leaf removal, shoot thinning, and a combination of both affect the grapevine (Vitis vinifera L. cv. Cabernet Sauvignon) yield components, berry composition, and flavonoid profile under context of climate change. First experiment assessed changes in the grape flavonoid content driven by four degrees of exposure. In the second experiment, individual grape berries subjected to different exposures were collected from two cultivars (Cabernet Sauvignon and Petit Verdot). The third experiment consisted of an experiment with three canopy management treatments (i) LR (removal of 5 to 6 basal leaves), (ii) ST (thinned to 24 shoots per vine), and (iii) LRST (a combination of LR and ST) and an untreated control (UNT). Berry composition, flavonoid content and profiles, and 3-isobutyl 2-methoxypyrazine were monitored during berry ripening. Although increasing canopy porosity through canopy management practices can be helpful for other purposes, this may not be the case of flavonoid compounds when a certain proportion of kaempferol was achieved. Our results revealed different sensitivities to degradation within the flavonoid groups, flavonols being the only monitored group that was upregulated by solar radiation. Within different canopy management practices, the main effects were due to the ST. Under environmental conditions given in this trial, ST and LRST hastened fruit maturity; however, a clear improvement of the flavonoid compounds (i.e., greater anthocyanin) was not observed at harvest. Methoxypyrazine berry content decreased with canopy management practices studied. Although some berry traits were improved (i.e. 2.5° Brix increase in berry total soluble solids) due to canopy management practices (ST), this resulted in a four-fold increase in labor operations cost, two-fold decrease in yield with a 10-fold increase in anthocyanin production cost per hectare that should be assessed together as the climate continues to get hot.

The mechanization of vineyard work originally led to a reduction in planting densities due to the lack of machinery adapted to the vineyard. The current availability of specific machinery makes it possible to establish higher planting densities. In this work, three planting densities (1.40×0.80 m, 1.80×1 m and 2.20×1.20 m, corresponding to 8928, 5555 and 3787 plants/ha respectively) were studied with four varieties autochthonous of Galicia (northwestern Spain): Albariño and Treixadura (white), Sousón and Mencía (red). The vines were trained in a vertical shoot positioning system using a single Royat cordon, and pruned to spurs with two buds each. Agronomic data (yield, pruning wood weight, Ravaz index) and oenological data in must were collected. The higher planting density (1.40×0.80 m) had no significant effect on grape yield per vine in white varieties, although production per hectare was much higher due to the greater number of plants. In red varieties, this planting density resulted in a significantly lower production per vine, compensated by the greater number of plants. In addition, it significantly reduced the Brix degree in the must of the Albariño, Treixadura and Sousón varieties, and increased the total acidity in the latter two and Mencía. It also caused an increase in extractable and total anthocyanins and IPT in red grapes. The effects of high planting density on grapes are of great interest for the adaptation of varieties in the context of climate change. In the future, it could be advisable to modify the limits imposed by the appellations of origin on the planting density of these varieties in order to obtain more balanced wines.

“Flavescence dorée” (FD) is a grapevine quarantine disease associated with phytoplasmas and transmitted to healthy plants by insect vectors, mainly Scaphoideus titanus. Infected plants usually develop symptoms of stunted growth, unripe cane wood, leaf rolling, leaf yellowing or reddening, and shrivelled berries. Since plants can remain symptomless up to four years, they may act as reservoirs of FD contributing to the spread of the disease. So far, conventional management strategies rely mainly on the insecticide treatments, uprooting of infected plants and use of phytoplasma-free propagation material. However, these strategies are costly and could have undesirable environmental impacts. Thus, the development of sustainable and noninvasive approaches for early detection of FD and its management are of great importance to reduce disease spread and select the best cultural practices and treatments. The present study aimed to evaluate if multispectral/hyperspectral technologies can be used to detect FD before the appearance of the first symptoms and if infected grapevines display a spectral imaging fingerprint. To that end, physiological parameters (leaf area, chlorophyll content and photosynthetic rate) were collected in concomitance to the measurements of plant reflectance (using both a portable apparatus and a remote sensing drone). Measurements were performed in two leaves of 8 healthy and 8 FD-infected grapevines, at four timepoints: before the development of disease symptoms (21st June); and after symptoms appearance (ii) at veraison (2nd August); at post-veraison (11th September); and at harvest (25th September). At all timepoints, FD infected plants revealed a significant decrease in the studied physiological parameters, with a positive correlation with drone imaging data and portable apparatus analyses. Moreover, spectra of either drone imaging and portable apparatus showed clear differences between healthy and FD-infected grapevines, validating multispectral/ hyperspectral technology as a potential tool for the early detection of FD or other grapevine-associated diseases.

Because terroir and cultivar are drivers of wine quality, is essential to investigate theirs effects on polyphenolic profile before promoting the implantation of a red minority variety in a specific area. This work, included in MINORVIN project, focuses in the polyphenolic profile of 7 red grapevines minority varieties of Vitis vinifera L. (Morate, Sanguina, Santafe, Terriza Tinta Jeromo Tortozona Tinta) and Tempranillo) from six typical viticulture Spanish areas: Aragón (A1), Cataluña (A2), Castilla la Mancha (A3), Castilla –León (A4), Madrid (A5) and Navarra (A6) of 2020 season. Polyphenolic substances were extracted from grapes. 35 compounds were identified and quantified (mg subtance/kg fresh berry) by HPLC and grouped in anthocyanins (ANT) flavanols (FLAVA), flavonols (FLAVO), hydroxycinnamic (AH), benzoic (BA) acids and stilbenes (ST). Antioxidant activity (AA, mmol TE /g fresh berry) was determined by DPPH method. The results were submitted to a two-way ANOVA to investigate the influence of variety, area and their interaction for each polyphenolic family and cluster analysis was used to construct hierarchical dendrograms, searching the natural groupings among the samples. Sanguina (A3) had the most of total polyphenols while Tempranillo (A5) those of ANT. Sanguina (A2) and (A3) reached the highest values of FLAVO, FLAVA and AA. These two last samples had also the maximum of AA. The effect cultivar and area were significant for all polyphenolic families analyzed. A high variability due to variety (>50%) was observed in FLAVA and the maximum value of variability due to growing area was detected in AA (86.41%), ANT and FLAVO (51%); the interaction variety*zone was significant only for ANT, FLAVO, EST and AA. Finally, dendrograms presented five cluster: i) Sanguina (A2); ii) Sanguina (A3); iii) Tempranillo (A5); iv) Tempranillo (A3); Terriza (A3,A5), Morate (A5,A6); v) Santafé (A1,A6); Tortozona tinta (A1,A3,A6); Tinta Jeromo (A3,A4).